Charles h



"2s be specifically 4 -charged,-'-sayr 600 pounds to I enema time '19, teen titans UNETED snares Parent tor-rice;

, emanates; n. 'rcnnnsr, or nanwatz, nanonn r. HAYDEN, or nanrran rownsnrr,

HIDDLE$EE (COUNTY, NEW JERSEY, AND GRIN R. DOUTHETT, 01F BEAVER FALLS, IENN$YLVANIA, ASSIGNORS JTO THE BARBER ASPHALT PAVING COMPANY, 01?

I PHKLADEEEHIA. PENNSYLVANIA, .A CORPORATEOIEL 015 WEST VTRGT lilllA.v

@riginal 'applicatibn filed August 28, 4 r

ernscnrrio rnon'ncrs.

- i 3, 1922. Serial No. 54 9,1236,

To whom it may concern Y Be it known that we, CinAnLns'N; Fonnnsr,

, I v of Rahway, in the county of Union and State of New Jersey, HAROLD P. HAYDEN, of

' s R-aritan Township, in the countyof Middlesex and State of New-Jersey, BLIIOl URHN R. Don'rrrnrr, of Beaver Falls, in the county of Beaver and State of; Pennsylvania, citizens of the United States, have invented certain 10 new and useful Improvements in Gilsonit'ic Products, whereof the following'is a specifi cation;

- Our invention relates to gilsonitic prodnets and their manufacture, and more: especially to productsand materials obtainable from gilsonit'e' through sulphonation treat- I menu We have found that there can be obtained from gilsonite-and gilsonit'ic substances semi-drying oils characterized by as various useful properties.

This application'is a divisipn of ourapplication, Serial No. 320,514, filed August 28, 1919, entitled Gilsonitic products and their manufacture.

The various escribed hereinafter. in accordance with-the best mode of applying them in a practical way at present known As a gilsonitic material-to betreated, we ordinarily prefer gilsonite distillate to native 'gilsonite itself. We have obtained a :much greater yield of sulphonic products from the treatment by preparing the dis- 't'illate sometime in advance and allowing it to'age fora considerable period before being treated. I Such distillatemay be prepared as follows:

Gilsonite as'received from the mine is 40 charged into an iron or-steel still, firedwith gas or oil (or otherwise suitably heated),

and connected to. a suitable condenser,

water-cooled."

such asan ironipipe condenser Any convenient quantity of gilsonite may be several! tons.

The still being closed and heat applied gradually, the'gilsonite will liquefy andcol lect in the bottom o f 'the still, and vapor and gas evolving from it will fill the top of the 5 still and'pass over into the condenser; As

the heating progresses,temperature-readings should taken from time to time on'the' ghases'of our invention will body of vapor in the upper portion of the still, as ,Well as on the body of-liquid' beneath it. (E'Xcepting as there may be spe cial'occasion for distinguishing them, we

here and hereinafter comprehend mingled" gases and vapors under the sin le term vapor, for the sake of brevity, or convenience, we refer to various stages otjopera 'tions. loythe corresponding vapor tempera tures, unless otherwis specially noted.)

till

The eil'ect' of the progressive heating of the gilsonite is togradually break it up and decompose it chemically,when ce, mainly, the

evolution of vapor. The coming ofi of vapor from-the still begins at atemperature of some 165, E, and continues up to or even beyond coking temperatures.

Up to the point where the vapor tempera ture approaches some 550 F, the distilla.

tion may be ,carriedout as-rapidly'asthe N contents of the still can be made to absorb heat. At this point, however, some exothermic or other peculiar action occurs, so that vthe evolution of vapor in the still tends to i become excessively rapid. Unless, therefore,

the." previous heating has been especially slow, it-is necessary to reduce the application of heating very greatly as this, critical point is approached, in. order 1 that undistilled liquid may not be carried'over into the condenser, and clog it up. so asto render inunusable; In practice, it will usually be found convenient tocut down the fire some- 100 F., in advance of this'teinperature. Once this critical point is well passed, the fire maybe increased and the distillation pushed on as measured on the solid coko product collectina" in the bottom of the still.

rapidly as desired to its conclusion. In

While the vapor coming. 0E from the still may all be led into the iron pipe condenser,

as above suggested, and all of thestrictly' vapo'nous portion thereof there condensed and collected as a liquid, a slightly difi'erent procedur'e is preferable. A minor portion of the vapor is 'condensa-ble at relatively high temperatures; and at the temperature in the co1 denser',-.th corresponding condensate is of such thick, gummy consistency that it would tend to clog it up. It is desirable,

Y collecte therefore, that this heavier portionofthe normall liquidproducts be condensed and separately, without entering the condenser at all. This can advantageously be taken care ofby making the pipe leading from the still to the condenser of substantial the pipe'(wh1ch length and providingit with a trap. With this arrangement, the heavier. portion of the roducts willbe condensed ect of the atmosphere upon normally liquid by the cooling e thus acts as a sort of auxiliary condenser), and will collect-in the trap,

whence it can be drawn ofl ,from time to time and added to the liquid products drawn from the condenser itself. The trap also affords a measure of protection against the efiects of too rapid-heating at the critical temperature above mentioned.

rectly, in gross, but to separate it into a plurality of difl'erent portions by fractionation or reduction. The following examples (wherein the temperatures given are...the

ing' from the still u vapor temperatures inthe still, unless otherwise stated) will sufficiently illustrate the most convenient methods of redistillation:

- (1 Condense separately the vapors come to 475 F. and from 475 to 600?" F.,-su sequently-drawing ofi as residuum the'oil unvaporized at the latter temperature, or allowing it tolremain and mix with the next charge of crude oil.

(2) 'Condense separately the vapors upto 475 F; from 475 F. to 650? F.;-and from 650 F.funtil the temperature of the mate-- rial in the bottom of the still is about 850 F. By this" procedure, an amount of coke e ual to about 2%.of the crudeoil charge wil be 7 produced.

through the. liquid in the still. Tnthis v "The gas ta ns In either of these cases, considerable de-' structive action occurs in the production ofv the higher fractions,,-especially the last. (3) Three fractions nearly .similarl' to' those described under (2) may lee-obtained at teniperatures'some 100 F. lower than those mentioned by carrying out the red s- 'ti-llation as described in U. S. Patent 877 ,620, g

"be obtained by startlngwlth relatively weak reagent, and, usingmore and more reactive granted January 28, 1908, to Wells, blowing carbon dioxide orother inert permanent gas case the destructive action is much less; It is advantageous to pass the gas and vapor :coming .oiflthrough-a .filter of fullers earth 4 in the dome of the still, on its way to the. condenser. A residuum of heavy oil willv preferably be left in the still, as described under- (1); i

from the primary distillation conammoma, which can be segregated as ammonium sulphate: by a sulphuric scrubbing operation. The coke from both distiljecting the purified perfectly of reagent equal to; 20% ,treated. Thus for the first treatment, the

-'reagent maybe oil of. vitriol alone; for the and 5 of-oil of, vitriol and oleum in equal parts; v

, Mam

lations also has a 'nitrogeneous content recoverable by, a similar operation in connection with conversion thereof-into fuel gas by incomplete gas-producer. The water eliminated from the crude distillate also contains ammonia converted into ammonium sulphate.

may be used the unconsumed portion of the combustion in a by-product 'in solution, which may, if desired be also For theseoperations for recovery of ammonia Q tion and sulphonation treatments herein after described; 7

Of-the distillates thus produced,we generally prefer to treat the intermediate one. Prior to sulphonation treatment, however, we-prefer to subject the gilsonitic material to preliminary purifying treatment with a sulphuric reagent, thus removing therefrom organic bases, olefines, and other impurities that might alter or impair the character and utility of the final products. inary sulphuric treatment may be carried out by agitation of the gilsonitic material with about 5% of sulphuric acid of oil of vitriol grade,1. e., about 66 B.,-for

This prelim-- about one half hour. It is desirable to repeat the'operation (using fresh acid) one or more tlmes.

After this preliminary step, sulphonation treatment may be carried out by-subilsonitic oil to the ac tion of a sulphonating reagent.-- The sulphonatingreagents which we prefer to use are oil of vitriol, such as mentioned above,

and fuming sulphuric acid or oleum. It

is desirable to conduct this treatment in a cast iron vessel, usingmechanical agitation rather than air agitation in order to avoid such contamination with atmospheric moisvture as mightinterfere with the desired re action.

We final products is improved by carrying out this treatment progressively, with successive portions of reagent, and segregating the reaction products, as formed, from the material being treated, so that eachiof the successively acting portions ofreagentshall be fresh and untainted with such reaction products. Furtherimprovement can or energeticreagent as the treatment-profour such treatments, each with an amount of the material second, a mixture of 15 parts. oil of vitriol parts Ioleum; for the third, a mixture have found that the quality the menses i for the fourth, a mixture or parts oil of vitrioland'lfi parts oleum. Each of these treatments may last about two hours.

If, on the other hand, it is desired to carry" out sulphonation treatment all at once, in a single operation, rather than progressively, it may be done bymec'hanical agitation forsome eight hours,using, say, an'amount' of sulphonating rea'gent equalto 80% of the material treated and'consisting of 50 parts oil of vitriol and 30 'partsoleum.

At the end of each treatment or operation," the charge in theagitator is allowed to stand 'an' hour or more, Whenit will be found to have separated into'two distinct layers; a

top layer of residual or mother oil, and a bottom layer of acid sludge. This latter treatment may be neutralized," as with.

should be drawn off and thus. segregated prior to the next treatment of the'mother material. The residual oil remaining'after the last sodium hydrate solution (preferably of specific gravity greater than 30 ea, in order to avoid .emulsification). excess of caustic has been drawn ofi, the resultant alkaline oil should preferably. not

be Washed, on account of its emulsifying tendency; but it may instead be distilled with steam, in order to improve its color, andfiltered through-'fullers earth for the same purpose. This gilsonitic sulphonatlon residual oil as thus purified is a thin, clear sired, the distillation above mentioned maybe carried out frac'tionally, so as to yield oil; substantiallycolorless, orderless, and tasteless and suitable for about the same uses .as highly refined petroleum. If dedifi'erent oils more especially suitable 'for' particular purposes.

It is preferable'that the lots of sludge obtained from different sulphonation treat ments be further treated or Worked up in-- 'dividually, since thevarious treatments yield final productsv having somewhat different properties. This sulphonation sludge contains, as principal components, unconsumed sulphonating reagent, Water-soluble organic some small amount of-other organic prod-'- ucts." The proportions of the sulphonic and other reaction products in different lots of sludge vary considerably; the oil reaction product, inparticular. may be entirely a osent from the sludge of the last sulphonation treatments.

in the sludge is that of solution in the uncon-' the useful properties of products resulting therefrom. We do not, however, mean The condition of the materials sumed sulphonating reagent.

We have found that. separation of the limit After the nation sludge oil is a viscous liquid; of

sulphonic material mentioned albove tron the rest or the sludge can be effected by ad dition thereto of a solvent of the sulphonating reagent: for this purpose, the sludge maybe diluted with an equal weighto'f water. lPreferably the water is placed in alead lined, water-jacketed vessel, and the i sludge gradually introduced at such a rate that the temperature shall not rise excessively, -llO'-- F,- being a perfectly safe The operation othermic, and sulphur. dioxide; is copiously evolved. The dilute sludge is allowed to stand some eight to"twelve hours,-more or less,at a temperature of 150911 or is decidedly 'exa thereabout. During this period, separation into three distinct layers takes place, and

these maybe successively drawn ed and thus segregated. f The bottom layerv is a. dilute aqueous solution of the excessbfsulphonathmg reagent, discolored by some slight amount of organic impurity; the middle layer commaterial, contaminated with an inconsiderable amo'untofthe solution that forms the ingredients of the top layer; and "the top prises the water-soluble organic sulphonic bottom layer'and with a small portion of th layer contains the reaction oil componentand the residual mother oil impurity, etc., mentmned-above. (In some cases, as indi- (bated-above, the top layer may entirely absent.)

- Coming, now, to the further dispositioni or treatment of these separationiproducts',

the dilute acid of thefbottom layer maybe used for the recovery of ammonia as a described. The top layer (when present) may be neutralized with sodium hydrate and washed with "water until free from I alkali. :The resulting gilsonitic sulphoslow-drying or semi-drying ..-'character;

"benzole' or naphtha and insoluble in alcohol, when freshly prepared; and vice-versa after sullicielntly prolonged exposure t'o-the 7 air. Not only 18' it adapted for general use; 1'15 as a semi-drying oil; but when mixed with.

boiled linseed oil, it so modifies the drying properties of the latter that itdries homo- ".geneously, without formation of the usualsurface film.v It also seems to render the elastic.

we have hereinbetore spoken of sulpho -nating reagents, ysulphonation treatment,

and enlphon'ation reaction or 'sulphonic products, etc, using these expression in reference, to the chemical character and mode of use of the reagent employed in the pr1ncipa'l treatment described above, or to fully. dried linseed oil tougher and more nets are true sulphonic substances in the sense of having sulphonic.radiculs,- since- We are wlthout clear evldence on th spomt.

Having thus described our invention, we clalm:

- 1. A semi-drying, viscous .gi lsonitic sulphonzition sludge '011.

.2. A gils'onitic oil; viscous endslo'w-oli y ing; soluble in benzole and naphtha. end

insoluble in alcoholwhen fresh, andvice versa, whendried.

.3. Aseml-drymg, viscous 'gilsonitic oil;

instead .ofwith a, surface fi Jim-testimony whereof, we have hereunto signed our names M; Maureen N. J, this 29th dayefMa-reh 1922.

CHARLES N. memes; I HARQLD 1P. HAYDEN. GRIN R. DQUTHET'JP.

Wifmesses:

D. J. Dmemomi,

Smmmmizzm D11 SAYNTO. 

